CN107369835B - Conductive adhesive for lithium ion battery and preparation method thereof, lithium ion battery electrode plate and preparation method thereof, and lithium ion battery - Google Patents
Conductive adhesive for lithium ion battery and preparation method thereof, lithium ion battery electrode plate and preparation method thereof, and lithium ion battery Download PDFInfo
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- H01M4/00—Electrodes
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The invention provides a conductive adhesive for a lithium ion battery, which comprises graphene and a first adhesive grafted on the surface of the graphene, wherein the first adhesive comprises at least one of polyvinyl alcohol, sodium carboxymethylcellulose, polyethylene glycol, polylactic acid, polymethyl methacrylate, polystyrene, polyvinylidene fluoride, hexafluoropropylene polymer, styrene-butadiene rubber, sodium alginate, starch, cyclodextrin and polysaccharide. The conductive adhesive for the lithium ion battery has good conductive performance and adhesive property, has certain strength and can enhance the overall mechanical strength of the electrode plate, and the conductive adhesive realizes that the adhesive and the conductive agent are combined into one, so that the content of active substances of the electrode plate can be improved, and the energy density of a battery core is further improved. The invention also provides a preparation method of the conductive adhesive, and an electrode plate and a lithium ion battery containing the conductive adhesive.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a conductive adhesive for a lithium ion battery and a preparation method thereof, a lithium ion battery electrode plate and a preparation method thereof, and the lithium ion battery.
Background
Lithium ion batteries have been widely used in the fields of portable electronic devices, electric vehicles, energy storage appliances, etc. because of their advantages of high energy density, long cycle life, and no maintenance.
In the existing lithium ion battery preparation process, active material (positive electrode or negative electrode active material) powder, a conductive agent and a binder are dispersed in a solvent to form slurry, and then the slurry is coated on a current collector (such as copper foil and aluminum foil) to form a pole piece, and finally a complete battery core is assembled. However, the existing commercial conductive agent mostly exists in the form of micron or even nano particles, and is not easy to disperse in the stirring process of slurry, so that excessive conductive agent is often required to be added in practice; not only does this reduce the cell energy density, but the excess conductive agent can also significantly reduce the first efficiency of the cell. In order to disperse the conductive agent in the solvent as much as possible, a sufficient amount of binder/dispersant needs to be added into the slurry, so that the conductivity of the pole piece prepared from the slurry is reduced, and the internal resistance of the cell is increased.
In addition, as the power consumption of portable electronic devices such as mobile phones and the like increases year by year, the market demand for high energy density lithium ion batteries is also more and more urgent. One of the technical solutions for significantly improving the energy density of the lithium ion battery is to replace the existing graphite cathode material with an alloy material such as silicon. However, the silicon material undergoes significant volume expansion (> 300%) during cycling, causing pulverization of the silicon particles and shedding from the current collector, resulting in rapid decay of the cycling performance of the cell. The solution in the industry at present comprises that a macromolecular compound which has carboxyl, hydroxyl and the like and can be combined with silicon-oxygen bonds on the surface of silicon is used as a binder and coated on the surface of silicon particles to restrict the pulverization and fragmentation of single silicon particles. However, the existing solution is only an improvement of the traditional binder, and a conductive agent such as carbon black is still required to be added; in addition, the binder molecules are small in size (nanoscale), and lack micron-scale rigid support, so that under the action of huge stress generated by volume expansion of silicon particles, the nanometer-scale binder molecules cannot restrict pulverization and fragmentation of the micron-scale silicon particles, so that the binder loses a binding effect after pulverization of a silicon negative electrode, and finally cycle performance of the battery core is rapidly attenuated.
Disclosure of Invention
In view of this, the first aspect of the present invention provides a conductive adhesive for a lithium ion battery, which has both good conductive performance and adhesive performance, and has a certain strength, so as to solve the problems of increased internal resistance of a battery cell, and reduced energy density and first efficiency of the battery cell caused by the need of using the adhesive and the conductive agent simultaneously in the existing lithium ion battery; and the existing binder molecules can not restrict the pulverization and fragmentation of the whole micron-scale silicon particles, so that the binder fails after the pulverization of the silicon cathode, and finally the cycle performance of the battery cell is rapidly attenuated.
In a first aspect, the present invention provides a conductive adhesive for a lithium ion battery, including graphene and a first adhesive grafted on a surface of the graphene, where the first adhesive includes at least one of polyvinyl alcohol (PVA), carboxymethylcellulose (CMC), polyethylene glycol (PEG), polylactic acid (PLA), polymethyl methacrylate (PMMA), Polystyrene (PS), polyvinylidene fluoride (PVdF), a hexafluoropropylene polymer, styrene-butadiene rubber (SBR), sodium alginate, starch, cyclodextrin, and polysaccharide.
In the first aspect of the present invention, when the first binder is at least one of polyvinyl alcohol, sodium carboxymethyl cellulose, polyethylene glycol, sodium alginate, starch, cyclodextrin, and polysaccharide, the conductive binder for a lithium ion battery further includes a second binder grafted to the surface of the graphene, the second binder being connected to the first binder by a chemical bond, and the second binder is at least one of polyacrylic acid (PAA) and Polyimide (PI).
In the first aspect of the present invention, the carboxyl groups in the first binder and the second binder are both alkali-metalized carboxyl groups.
In the first aspect of the present invention, the graphene particles have a thickness of 0.35 to 50nm and a D50 particle size of 50 to 5000 nm.
In the first aspect of the present invention, the graphene accounts for 0.1 to 10% of the total mass of the conductive binder for a lithium ion battery.
In the first aspect of the present invention, the first binder accounts for 20 to 50% of the total mass of the first binder and the second binder.
The conductive adhesive for the lithium ion battery has good conductivity and adhesive property and certain strength, so that the conductive adhesive not only can improve the conductivity of an electrode plate, but also can realize better effect of combining with active substances (such as lithium cobaltate, graphite, silicon and the like) under the condition of low addition amount, greatly reduce the internal resistance of a battery cell and effectively inhibit the pulverization of the active substances; in addition, the conductive adhesive realizes the combination of the adhesive and the conductive agent, thereby improving the content of active substances of the pole piece and further improving the energy density of the battery cell.
In a second aspect, the invention provides a preparation method of the conductive adhesive for the lithium ion battery, which comprises the following steps:
carrying out oxidation treatment on graphene to obtain graphene oxide; taking a first binder, and grafting the first binder to the surface of the graphene oxide through a condensation reaction; or taking a monomer of a first binder, and polymerizing and grafting the monomer of the first binder to the surface of the graphene oxide through atom transfer radical polymerization reaction to obtain graphene grafted and modified by the first binder, so as to obtain the conductive binder for the lithium ion battery; the first binder comprises at least one of polyvinyl alcohol, carboxymethyl cellulose, polyethylene glycol, polylactic acid, polymethyl methacrylate, polystyrene, polyvinylidene fluoride, hexafluoropropylene polymer, styrene-butadiene rubber, sodium alginate, starch, cyclodextrin and polysaccharide.
In the second aspect of the present invention, when the first binder is at least one of polyvinyl alcohol, sodium carboxymethyl cellulose, polyethylene glycol, sodium alginate, starch, cyclodextrin and polysaccharide, the method further includes, after the first binder graft-modified graphene is obtained, taking a monomer of a second binder, and grafting the monomer of the second binder onto the first binder graft-modified graphene in an in-situ polymerization manner under the action of an initiator, wherein the second binder is connected with the first binder through a chemical bond, so as to obtain the conductive binder for the lithium ion battery; the second binder is at least one of polyacrylic acid and polyimide.
In the second aspect of the present invention, the initiator is selected from at least one of ammonium persulfate, alkali metal persulfate, Azobisisobutyronitrile (AIBN), Benzoyl Peroxide (BPO), azobisisobutylamidine hydrochloride (AIBA), azobiscyanovaleric acid (ACVA), and Azobisisopropylimidazoline (AIP).
In the second aspect of the present invention, when the first binder includes polylactic acid, or when the second binder includes polyacrylic acid, the alkali-metallizing treatment of the carboxyl group in the polylactic acid or polyacrylic acid with an aqueous solution of an alkali metal hydroxide is further included.
The preparation method of the conductive adhesive for the lithium ion battery provided by the second aspect of the invention has the advantages of simple and feasible process and low cost.
In a third aspect, the present invention provides an electrode plate for a lithium ion battery, including a current collector, an electrode active material coated on the current collector, and the conductive adhesive for a lithium ion battery according to the first aspect of the present invention. In the electrode plate of the lithium ion battery, the conductive adhesive for the lithium ion battery accounts for 0.5-10% of the total mass of the electrode active material and the conductive adhesive for the lithium ion battery.
The electrode plate of the lithium ion battery provided by the third aspect of the invention has good conductivity, strong mechanical property, high content of active substances and strong adhesive force on the surface of the current collector.
In a fourth aspect, the invention provides a preparation method of an electrode plate of a lithium ion battery, which comprises the following steps:
taking a current collector, adding an electrode active material and the conductive adhesive for the lithium ion battery in the first aspect of the invention into a solvent, uniformly mixing to obtain slurry, coating the slurry on the current collector, drying at 90-120 ℃, and pressing to obtain an electrode plate of the lithium ion battery.
In a fifth aspect, the present invention provides a lithium ion battery, which comprises the conductive adhesive for lithium ion batteries according to the first aspect of the present invention. The lithium ion battery has higher energy density and good cycle performance.
Advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the invention.
Drawings
Fig. 1 is a schematic structural diagram of a conductive adhesive for a lithium ion battery according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a conductive adhesive for a lithium ion battery according to another embodiment of the present invention;
FIG. 3 is a schematic diagram showing the effect of the conductive adhesive for lithium ion batteries of the present invention in inhibiting the pulverization and expansion of silicon particles;
fig. 4 is a flow chart illustrating a process of synthesizing a conductive adhesive for a lithium ion battery according to an embodiment of the present invention.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and improvements without departing from the principle of the embodiments of the present invention, and such modifications and improvements are considered to be within the scope of the embodiments of the present invention.
At present, in a lithium ion battery preparation process, in order to obtain an electrode plate with good performance, a binder and a conductive agent are generally required to be added during preparation of slurry, however, the addition of the components can increase the internal resistance of a battery cell, and reduce the energy density and the first efficiency of the battery cell; in order to solve the problem, the industry tries to coat the silicon particles with macromolecular compounds which are provided with carboxyl, hydroxyl and the like and can be combined with silicon-oxygen bonds on the silicon surface as binders to restrict the pulverization and fragmentation of single silicon particles. However, the effect is not very desirable because such a binder has a small molecular size (nano-scale) and binds only pulverization on the surface of silicon particles in a micro-scale, but does not significantly contribute to pulverization separation inside and between macro-micro-scale silicon particles, and thus expansion pulverization of silicon or tin alloy cannot be well suppressed. In order to solve the above problems, embodiments of the present invention provide a conductive adhesive for a lithium ion battery, which has both good conductive performance and adhesive performance and has a certain strength.
Specifically, the embodiment of the invention provides a conductive adhesive for a lithium ion battery, which comprises graphene and a first adhesive grafted on the surface of the graphene, wherein the first adhesive comprises at least one of polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), polyethylene glycol (PEG), polylactic acid (PLA), polymethyl methacrylate (PMMA), Polystyrene (PS), polyvinylidene fluoride (PVdF), hexafluoropropylene polymer, styrene-butadiene rubber (SBR), sodium alginate, starch, cyclodextrin and polysaccharide. Wherein the hexafluoropropylene polymer comprises polyvinylidene fluoride-hexafluoropropylene, hexafluoropropylene dimer and hexafluoropropylene polymer. Fig. 1 is a schematic structural view of the conductive adhesive for a lithium ion battery according to the present embodiment. As shown in fig. 1, the black portion on the left side in the figure is a graphene matrix, and B1 is a polymer segment of the first binder.
According to the conductive adhesive for the lithium ion battery, provided by the embodiment of the invention, the conductivity of the electrode plate is improved and the integral mechanical strength of the electrode plate is enhanced by introducing the graphene framework; the high-molecular binder is grafted on the surface of the graphene, so that a better effect of combining with active substances (such as lithium cobaltate, graphite, silicon and the like) can be realized under the condition of low addition of the conductive binder.
In another embodiment of the present invention, when the first binder is at least one of polyvinyl alcohol, sodium carboxymethyl cellulose, polyethylene glycol, sodium alginate, starch, cyclodextrin and polysaccharide, the conductive binder for a lithium ion battery further includes a second binder grafted to the surface of the graphene, the second binder being connected to the first binder by a chemical bond, and the second binder is at least one of polyacrylic acid (PAA) and Polyimide (PI). The second binder can further effectively suppress the expansion of the active material such as silicon particles. Fig. 2 is a schematic structural view of the conductive adhesive for a lithium ion battery in the present embodiment. As shown in fig. 2, the black part on the left side in the figure is a graphene matrix, B1 is a polymer segment of a first binder, and B2 is a polymer segment of a second binder.
In an embodiment of the present invention, the carboxyl groups in the first binder and the second binder are both alkali-metalized carboxyl groups. After the carboxyl groups in the first binder and the second binder are neutralized to form carboxylate, the carboxylate loses acidity, so that the subsequent reaction with lithium hexafluorophosphate in the electrolyte when the carboxylate is used in a lithium ion battery is avoided.
In the embodiment of the invention, the thickness of the graphene particles is 0.35-50nm, and the particle size of D50 is 50-5000 nm. In a preferred embodiment of the present invention, the graphene particles have a thickness of 5nm and a D50 particle size of 100 nm. By selecting the graphene with a proper size, the dispersion is facilitated, the good conductivity is provided, and the conductive adhesive can obtain a certain strength.
In the embodiment of the present invention, the graphene may be conventional graphene or doped graphene, and the doping element in the doped graphene may include at least one of N, B, P, S, F, Cl, and O. The graphene may be single-layer graphene or multi-layer graphene.
In the embodiment of the invention, the graphene accounts for 0.1-10%, preferably 0.5-10% of the total mass of the conductive binder for the lithium ion battery.
In the embodiment of the invention, when the graphene surface is grafted with the first binder and the second binder simultaneously, the first binder accounts for 20-50% of the total mass of the first binder and the second binder.
To more clearly illustrate the effect of the conductive binder for lithium ion batteries of the embodiment of the present invention in inhibiting the pulverization and expansion of silicon particles, please refer to the schematic effect diagram of fig. 3. In fig. 3, 1 is a silicon particle, 2 is graphene, and 3 is a binder molecular chain grafted on the graphene. As shown in fig. 3, the silicon particles are confined within a hollow space structure built up by graphene sheets; hydrogen bonds formed among functional groups such as hydroxyl groups and carboxyl groups on a high molecular chain of the adhesive grafted on the surfaces of the graphene sheets form strong combination between adjacent graphene sheets; thus, when the silicon particle is greatly expanded, the graphene sheets around the silicon particle are not completely separated from each other. When the silicon particles are expanded by embedding lithium, the polymer chains of the binding agent are stretched, and a stress release space is provided for volume expansion; when the silicon particles are subjected to lithium removal and shrinkage, the polymer chains of the binder are wound and shrunk again, so that the graphene and the silicon are always kept in contact. In addition, the high molecular chain of the binder is always covered on the surface of the silicon particles, so that the surface layer of the silicon particles is not separated from the main body after being pulverized, and finally, the pulverization and expansion of the silicon particles are effectively inhibited.
The conductive adhesive for the lithium ion battery has good conductivity and adhesive property and certain strength, so that the conductive adhesive not only can improve the conductivity of an electrode plate, but also can realize better effect of combining with active substances (such as lithium cobaltate, graphite, silicon and the like) under the condition of low addition amount, greatly reduce the internal resistance of a battery cell and effectively inhibit the pulverization of the active substances of the electrode; in addition, the conductive adhesive realizes the combination of the adhesive and the conductive agent, thereby improving the content of active substances of the pole piece and further improving the energy density of the battery cell.
The conductive adhesive for the lithium ion battery provided by the embodiment of the invention can be used for the negative electrode of the lithium ion battery and can also be used for the positive electrode. The conductive binder for the lithium ion battery provided by the embodiment of the invention is applied to the traditional graphite cathode or anode, so that the conductive performance of the electrode and the binding performance of particles can be enhanced, the internal resistance of the battery is reduced, and the rate capability and the cycle performance of the battery are improved; when the graphene oxide/tin oxide composite conductive adhesive is applied to a silicon, tin or alloy negative electrode, the graphene skeleton in the conductive adhesive also plays a role in wrapping particles and providing rigid support for the adhesive, so that the protection effect of expansion and pulverization of the negative electrode is limited, and the cycling stability of the silicon, tin or alloy negative electrode is effectively improved finally.
Correspondingly, the embodiment of the invention provides a preparation method of the conductive adhesive for the lithium ion battery, which comprises the following steps:
carrying out oxidation treatment on graphene to obtain graphene oxide; taking a first binder, and grafting the first binder to the surface of the graphene oxide through a condensation reaction; or taking a monomer of a first binder, and polymerizing and grafting the monomer of the first binder to the surface of the graphene oxide through atom transfer radical polymerization reaction to obtain graphene grafted and modified by the first binder, so as to obtain the conductive binder for the lithium ion battery; the first binder comprises at least one of polyvinyl alcohol, carboxymethyl cellulose, polyethylene glycol, polylactic acid, polymethyl methacrylate, polystyrene, polyvinylidene fluoride, hexafluoropropylene polymer, styrene-butadiene rubber, sodium alginate, starch, cyclodextrin and polysaccharide.
Specifically, for method 1: taking a first binder, and grafting the first binder to the surface of the graphene oxide through a condensation reaction. The method is suitable for grafting polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), polyethylene glycol (PEG), sodium alginate, starch, cyclodextrin and polysaccharide.
For method 2: taking a monomer of a first binder, and polymerizing and grafting the monomer of the first binder to the surface of the graphene oxide through atom transfer radical polymerization reaction. The method is suitable for grafting of polylactic acid (PLA), polymethyl methacrylate (PMMA), Polystyrene (PS), polyvinylidene fluoride (PVdF), hexafluoropropylene polymer (HFP) and styrene-butadiene rubber (SBR). The monomer of the second binder comprises lactic acid, methyl methacrylate, styrene, vinylidene fluoride, hexafluoropropylene and butadiene.
In the embodiment of the present invention, the specific reaction conditions, including the solvent, the reaction temperature, the reaction time, and the like, required for the condensation reaction and the atom transfer radical polymerization reaction may be determined according to the specific type of the first binder to be grafted, and the present invention is not particularly limited.
In the embodiment of the present invention, the oxidation treatment is specifically performed by: heating graphene to 50-95 ℃ in a strong oxidant aqueous solution or atmosphere to form graphene oxide; the strong oxidant is at least one selected from sulfuric acid, nitric acid, perchloric acid, ammonium persulfate, alkali permanganate, alkali dichromate, hydrogen peroxide and ozone. The surface of graphene oxide has a large number of carboxyl functional groups.
In the embodiment of the invention, when the first binder is at least one of polyvinyl alcohol, sodium carboxymethylcellulose, polyethylene glycol, sodium alginate, starch, cyclodextrin and polysaccharide, taking a monomer of a second binder after the first binder is obtained and grafted with the modified graphene, and grafting the monomer of the second binder onto the first binder grafted and modified graphene in an in-situ polymerization manner under the action of an initiator, wherein the second binder is connected with the first binder through a chemical bond to obtain the conductive binder for the lithium ion battery; the second binder is at least one of polyacrylic acid and polyimide.
In an embodiment of the present invention, the initiator is at least one selected from the group consisting of ammonium persulfate, alkali metal persulfate, Azobisisobutyronitrile (AIBN), Benzoyl Peroxide (BPO), azobisisobutylamidine hydrochloride (AIBA), azobiscyanovaleric acid (ACVA), and Azobisisopropylimidazoline (AIP). If the initiator is persulfate, sodium bisulfite is used as an auxiliary agent, and the mass ratio of the persulfate to the sodium bisulfite is 100:1-1: 1.
In an embodiment of the present invention, when the first binder includes polylactic acid, or when the second binder includes polyacrylic acid, the method further includes alkali-metallizing a carboxyl group in the polylactic acid or the polyacrylic acid with an aqueous solution of an alkali metal hydroxide. The aqueous alkali metal hydroxide solution may be lithium hydroxide, sodium hydroxide, potassium hydroxide. The system pH is neutralized to 6-7 with an aqueous alkali metal hydroxide solution to form a carboxylate.
The preparation method of the conductive adhesive for the lithium ion battery provided by the embodiment of the invention has the advantages of simple and feasible process and low cost.
In addition, the embodiment of the invention also provides a lithium ion battery electrode plate which comprises a current collector, an electrode active material coated on the current collector and the conductive adhesive for the lithium ion battery. In the electrode plate of the lithium ion battery, the conductive adhesive for the lithium ion battery accounts for 0.5-10%, preferably 2-5% of the total mass of the electrode active material and the conductive adhesive for the lithium ion battery.
The lithium ion battery electrode piece provided by the embodiment of the invention has good conductivity, strong mechanical property, high active substance content and strong adhesive force on the surface of the current collector.
Correspondingly, the embodiment of the invention also provides a preparation method of the electrode plate of the lithium ion battery, which comprises the following steps:
taking a current collector, adding an electrode active material and the conductive adhesive for the lithium ion battery in the embodiment of the invention into a solvent, uniformly mixing to obtain slurry, coating the slurry on the current collector, drying at 90-120 ℃, and pressing to obtain the electrode plate of the lithium ion battery.
The conductive binder for the lithium ion battery accounts for 0.5-10%, preferably 2-5% of the total mass of the electrode active material and the conductive binder for the lithium ion battery. The electrode pole piece of the lithium ion battery can be pressed into a required thickness which can be 0.05-0.15 mm. The solvent includes water, N-methylpyrrolidone (NMP), and the like.
Finally, the embodiment of the invention provides a lithium ion battery, which comprises the conductive adhesive for the lithium ion battery. The lithium ion battery has higher energy density and good cycle performance.
The following examples are intended to illustrate the invention in more detail. The embodiments of the present invention are not limited to the following specific embodiments. The present invention can be modified and implemented as appropriate within the scope of the main claim.
Example one
A preparation method of a conductive adhesive for a lithium ion battery comprises the following steps:
(1) weighing 10G of graphene, mixing with 100G of concentrated nitric acid (65 wt%) aqueous solution, heating to 95 ℃, stirring for 4 hours, washing with water, and drying to obtain a graphene oxide sample G;
(2) adding 10G of graphene oxide sample G into 100ml of dimethyl sulfoxide (DMSO), adding 2G of thionyl chloride, stirring and reacting for 2h at room temperature, washing with DMSO after the reaction is finished, dispersing in DMSO again, adding 2G of PVA, stirring for 2h at 120 ℃, washing and drying to obtain PVA graft modified graphene G-PVA;
(3) dispersing G-PVA in water, introducing nitrogen to remove oxygen, adding 2G acrylic acid and 0.1G K while stirring2S2O8With 0.03g NaHSO3Heating to 55 deg.C, reactingAfter the reaction is finished for 2-4h, washing with water and drying to obtain polyvinyl alcohol-polyacrylic acid (PVA-PAA) grafted graphene G-PVA-b-PAA;
(4) dispersing G-PVA-b-PAA in water, adding LiOH aqueous solution to neutralize until the pH value is 6 to 6, washing with water and drying to obtain a final product G-PVA-b-PAALi, namely the conductive adhesive for the lithium ion battery.
The product can be used as a conductive agent and a binder in the preparation process of slurry of negative electrode materials such as graphite, silicon and alloy thereof of a lithium ion battery.
Fig. 4 is a flow chart illustrating the synthesis of the conductive adhesive for lithium ion batteries according to the present embodiment. G-PVA-b-PAALi with different values of a, b and n can be obtained by changing the material ratio, and the like, wherein the value range of a is 50-100000, the value range of b is 50-100000, and the value range of n is 100-200000. Preferably, the value range of a is 500-.
Preparing a lithium ion battery: uniformly mixing a silicon negative electrode material (with the particle size of 100nm) and the conductive binder G-PVA-b-PAALi for the lithium ion battery prepared in the embodiment in water according to the mass ratio of 93:7 to obtain negative electrode slurry, coating the obtained negative electrode slurry on a copper foil current collector, drying the copper foil current collector in vacuum at 110 ℃ to obtain a negative electrode plate, and assembling the negative electrode plate into a button cell in a glove box for testing, wherein the electrode is made of lithium metal, the diaphragm is celgard C2400, and the electrolyte is 1.3M LiPF6The EC, PC and DEC (volume ratio of 3:1:6) solutions of (C).
Example two
A preparation method of a conductive adhesive for a lithium ion battery comprises the following steps:
(1) weighing 10G of graphene, mixing with 100G of concentrated nitric acid (65 wt%) aqueous solution, heating to 95 ℃, stirring for 4 hours, washing with water, and drying to obtain a graphene oxide sample G.
(2) Dispersing 10g of graphene oxide in 100ml of Tetrahydrofuran (THF) under stirring, adding 1g of diborane, stirring at room temperature for 12 hours, and reducing carboxyl, anhydride, carbonyl and the like on the surface of the graphene oxide into alcoholic hydroxyl; then washing with THF, drying, dispersing again in a mixed solution of 2G of pyridine and 100mL of dry ether, adding 2G of 2-bromoisobutyl acyl bromide (BiBB), slowly stirring at 0 ℃ for 2h, then stirring at room temperature for reaction for 10h, washing with absolute ethanol, and drying to obtain hydroxyl-brominated graphene oxide G-Br;
(3) adding 100mL of methanol, 3g of vinylidene fluoride, 0.02g of cuprous bromide (CuBr) and 0.05g of 2, 2' -bipyridine (Bpy) into a reactor, and carrying out argon bubbling for 30min at room temperature to remove oxygen in the system; and then adding the G-Br powder under the protection of argon, stirring the mixture in a closed reactor at room temperature to react for 24 hours, filtering the mixture after the reaction, washing the mixture with anhydrous methanol and drying the mixture to obtain a polyvinylidene fluoride grafted and modified graphene sample G-PVdF, thus obtaining the conductive adhesive for the lithium ion battery.
The product can be used as a conductive agent and a binder in the preparation process of slurry of a lithium ion battery anode material and a graphite cathode material.
Preparing a lithium ion battery: lithium cobaltate and the conductive binder G-PVdF powder for the lithium ion battery prepared in the embodiment are mixed according to a mass ratio of 93:7 evenly mixing the materials in N-methyl pyrrolidone (NMP) to obtain positive electrode slurry, coating the obtained positive electrode slurry on an aluminum foil current collector, drying the aluminum foil current collector in vacuum at 120 ℃ to obtain a positive electrode plate, and assembling the positive electrode plate into a button cell in a glove box for testing, wherein the electrode adopts lithium metal, the diaphragm is celgard C2400, and the electrolyte is 1.3M LiPF6The EC, PC and DEC (volume ratio of 3:1:6) solutions of (C).
EXAMPLE III
A preparation method of a conductive adhesive for a lithium ion battery comprises the following steps:
(1) weighing 10G of graphene, mixing with 100G of concentrated nitric acid (65 wt%) aqueous solution, heating to 95 ℃, stirring for 4 hours, washing with water, and drying to obtain a graphene oxide sample G;
(2) adding 10G of graphene oxide sample G into 200ml of dimethyl sulfoxide (DMSO), adding 15G of thionyl chloride, stirring and reacting for 4h at room temperature, washing with DMSO after the reaction is finished, dispersing in DMSO again, adding 3G of sodium carboxymethylcellulose, stirring for 6h at 120 ℃, washing with water, and drying to obtain sodium carboxymethylcellulose-grafted and modified graphene G-CMC;
the product can be used as a conductive agent and a binder in the preparation process of slurry of negative electrode materials such as graphite, silicon and alloy thereof of a lithium ion battery.
Preparing a lithium ion battery: uniformly mixing a silicon negative electrode material (with the particle size of 100nm) and the conductive binder G-PVA-b-PAALi for the lithium ion battery prepared in the embodiment in water according to the mass ratio of 93:7 to obtain negative electrode slurry, coating the obtained negative electrode slurry on a copper foil current collector, drying the copper foil current collector in vacuum at 110 ℃ to obtain a negative electrode plate, and assembling the negative electrode plate into a button cell in a glove box for testing, wherein the electrode is made of lithium metal, the diaphragm is celgard C2400, and the electrolyte is 1.3M LiPF6The EC, PC and DEC (volume ratio of 3:1:6) solutions of (C).
Example four
A preparation method of a conductive adhesive for a lithium ion battery comprises the following steps:
(1) weighing 10G of graphene, mixing with 100G of concentrated nitric acid (65 wt%) aqueous solution, heating to 95 ℃, stirring for 4 hours, washing with water, and drying to obtain a graphene oxide sample G.
(2) Dispersing 10g of graphene oxide in 100ml of Tetrahydrofuran (THF) under stirring, adding 1g of diborane, stirring at room temperature for 12 hours, and reducing carboxyl, anhydride, carbonyl and the like on the surface of the graphene oxide into alcoholic hydroxyl; then washing with THF, drying, dispersing again in a mixed solution of 2G of pyridine and 100mL of dry ether, adding 2G of 2-bromoisobutyl acyl bromide (BiBB), slowly stirring at 0 ℃ for 2h, then stirring at room temperature for reaction for 10h, washing with absolute ethanol, and drying to obtain hydroxyl-brominated graphene oxide G-Br;
(3) adding 100mL of methanol, 4g of methyl methacrylate, 0.03g of cuprous bromide (CuBr) and 0.06g of 2, 2' -bipyridine (Bpy) into a reactor, and carrying out argon bubbling at room temperature for 30min to remove oxygen in the system; and then adding the G-Br powder under the protection of argon, stirring the mixture in a closed reactor at room temperature to react for 18 hours, filtering the mixture after the reaction, washing the mixture with anhydrous methanol and drying the mixture to obtain a polymethyl methacrylate grafted and modified graphene sample G-PMMA, thus obtaining the conductive adhesive for the lithium ion battery.
The product can be used as a conductive agent and a binder in the preparation process of slurry of negative electrode materials such as graphite, silicon and alloy thereof of a lithium ion battery.
Preparing a lithium ion battery: uniformly mixing a silicon negative electrode material (with the particle size of 100nm) and the conductive binder G-PVA-b-PAALi for the lithium ion battery prepared in the embodiment in water according to the mass ratio of 93:7 to obtain negative electrode slurry, coating the obtained negative electrode slurry on a copper foil current collector, drying the copper foil current collector in vacuum at 110 ℃ to obtain a negative electrode plate, and assembling the negative electrode plate into a button cell in a glove box for testing, wherein the electrode is made of lithium metal, the diaphragm is celgard C2400, and the electrolyte is 1.3M LiPF6The EC, PC and DEC (volume ratio of 3:1:6) solutions of (C).
Effects of the embodiment
In order to strongly support the beneficial effects brought by the technical scheme of the embodiment of the invention, the following performance tests are provided:
testing the charge-discharge efficiency and the capacity retention rate for the first time:
(1) the button cell of the example was charged to a voltage of 0.001V at a current of 100mA/1g active material, followed by constant voltage until the current was less than 10mA/1g active material; laying aside for 10 mins; the button cells were then discharged to 2.5V at a current of 100mA/1g active material. The completion of the charging and discharging process is recorded as 1 charging/discharging cycle. The first charge-discharge capacity and the charge-discharge capacity of 50 cycles of charge-discharge of the battery were recorded.
(2) The button cell of example two was charged to a voltage of 4.4V at a current of 100mA/1g active material, followed by constant voltage until the current was less than 10mA/1g active material; laying aside for 10 mins; the button cells were then discharged to 3.0V at a current of 100mA/1g active material. The completion of the charging and discharging process is recorded as 1 charging/discharging cycle. The first charge-discharge capacity and the charge-discharge capacity of 50 cycles of charge-discharge of the battery were recorded.
The formulas for the first coulombic efficiency and the capacity retention of the battery are respectively as follows:
first coulombic efficiency (%) -first discharge capacity/first charge capacity × 100%;
the capacity retention (%) of the nth cycle was equal to the discharge capacity of the nth cycle/the discharge capacity of the 1 st cycle × 100%.
The test results of the first charge-discharge efficiency and capacity retention rate of the button cells of the first and second examples are shown in table 1:
TABLE 1
Therefore, the conductive adhesive for the lithium ion battery prepared by the embodiment of the invention can effectively buffer the negative influence caused by the volume change of the active material in the charging and discharging processes, and improve the cycle characteristics of the battery, and can be used as a conductive agent and an adhesive simultaneously, so that the content of the positive and negative lithium-embedded active substances can be improved, and the energy density of a battery core can be further improved.
Claims (9)
1. The conductive adhesive for the lithium ion battery is characterized by consisting of graphene, a first adhesive grafted on the surface of the graphene and a second adhesive grafted on the surface of the graphene, wherein the second adhesive is connected with the first adhesive through a chemical bond, the first adhesive is at least one of polyvinyl alcohol, sodium carboxymethyl cellulose, polyethylene glycol, sodium alginate, starch, cyclodextrin and polysaccharide, the second adhesive is at least one of polyacrylic acid and polyimide, carboxyl in the second adhesive is alkali metallization carboxyl, the thickness of graphene particles is 5nm-50nm, and the particle size of D50 is 50nm-5000 nm.
2. The conductive binder for lithium ion batteries according to claim 1, wherein the graphene accounts for 0.1 to 10% of the total mass of the conductive binder for lithium ion batteries.
3. The conductive adhesive for lithium ion batteries according to claim 1, wherein the first adhesive accounts for 20 to 50% of the total mass of the first adhesive and the second adhesive.
4. A preparation method of a conductive adhesive for a lithium ion battery is characterized by comprising the following steps:
carrying out oxidation treatment on graphene to obtain oxidized graphene, wherein the thickness of graphene particles is 5nm-50nm, and the particle size of D50 is 50nm-5000 nm; taking a first binder, and grafting the first binder to the surface of the graphene oxide through a condensation reaction; or taking a monomer of a first binder, and polymerizing and grafting the monomer of the first binder to the surface of the graphene oxide through atom transfer radical polymerization reaction to obtain the first binder graft modified graphene oxide; the first binder is at least one of polyvinyl alcohol, sodium carboxymethylcellulose, polyethylene glycol, sodium alginate, starch, cyclodextrin and polysaccharide;
taking a monomer of a second adhesive, and under the action of an initiator, in-situ polymerizing and grafting the monomer of the second adhesive to the graphene oxide grafted and modified by the first adhesive, wherein the second adhesive is connected with the first adhesive through a chemical bond to obtain the conductive adhesive for the lithium ion battery, the second adhesive is at least one of polyacrylic acid and polyimide, and when the second adhesive is polyacrylic acid, alkali metallization treatment is further performed on carboxyl in the polyacrylic acid by adopting an alkali metal hydroxide aqueous solution.
5. The method of preparing a conductive adhesive for a lithium ion battery according to claim 4, wherein the initiator is at least one selected from the group consisting of ammonium persulfate, alkali metal persulfate, azobisisobutyronitrile, benzoyl peroxide, azobisisobutylamidine hydrochloride, azobiscyanovaleric acid, and azobisisopropylimidazoline.
6. A lithium ion battery electrode piece, which is characterized by comprising a current collector, an electrode active material coated on the current collector and the conductive adhesive for the lithium ion battery of any one of claims 1 to 3.
7. The lithium ion battery electrode sheet according to claim 6, wherein the conductive binder for lithium ion batteries accounts for 0.5 to 10% of the total mass of the electrode active material and the conductive binder for lithium ion batteries.
8. A preparation method of an electrode plate of a lithium ion battery is characterized by comprising the following steps:
taking a current collector, adding an electrode active material and the conductive adhesive for the lithium ion battery as claimed in any one of claims 1 to 3 into a solvent, uniformly mixing to obtain slurry, coating the slurry on the current collector, drying at 90-120 ℃, and pressing to obtain the electrode plate of the lithium ion battery.
9. A lithium ion battery comprising the conductive binder for lithium ion batteries according to any one of claims 1 to 3.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610318938.7A CN107369835B (en) | 2016-05-12 | 2016-05-12 | Conductive adhesive for lithium ion battery and preparation method thereof, lithium ion battery electrode plate and preparation method thereof, and lithium ion battery |
| PCT/CN2016/108780 WO2017193571A1 (en) | 2016-05-12 | 2016-12-07 | Conductive adhesive for lithium-ion battery and preparation method therefor, lithium-ion battery electrode plate and preparation method therefor, and lithium-ion battery |
| EP16901526.0A EP3444881B1 (en) | 2016-05-12 | 2016-12-07 | Conductive adhesive for lithium-ion battery and preparation method therefor, lithium-ion battery electrode plate and preparation method therefor, and lithium-ion battery |
| US16/189,432 US11024873B2 (en) | 2016-05-12 | 2018-11-13 | Lithium-ion battery conductive bonding agent and production method thereof, lithium-ion battery electrode plate and production method thereof, and lithium-ion battery |
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| CN201610318938.7A CN107369835B (en) | 2016-05-12 | 2016-05-12 | Conductive adhesive for lithium ion battery and preparation method thereof, lithium ion battery electrode plate and preparation method thereof, and lithium ion battery |
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| EP3444881A1 (en) | 2019-02-20 |
| EP3444881B1 (en) | 2023-06-21 |
| WO2017193571A1 (en) | 2017-11-16 |
| CN107369835A (en) | 2017-11-21 |
| US20190081350A1 (en) | 2019-03-14 |
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| EP3444881A4 (en) | 2019-03-13 |
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